JP2824717B2 - Processing method of silver halide photographic material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for processing a silver halide photographic light-sensitive material, and more particularly to a highly stable processing.

[0002]

2. Description of the Related Art Silver halide photographic materials are used in the field of plate making,
It is used in a wide range of fields such as the field of medical diagnosis. As the fields of use have been expanded and deepened, the demand for development processing steps required for image formation has increased. In particular, rapid and stable development processing has been strongly desired. After exposure, the silver halide photographic material is generally processed in the steps of developing, fixing and washing with water. Above all, the black-and-white developer is generally an alkaline solution containing a hydroquinone as a developing agent, an aminophenol or 3-pyrazolidone as an auxiliary developing agent, and a sulfite.

The sulfite is used in the form of an alkali metal sulfite or bisulfite, and is an essential component for maintaining the developing activity of hydroquinones and for suppressing the air oxidation of the developer. is there. Further, sulfites have an action of appropriately dissolving silver halide, and are sometimes used in a method of improving the graininess by positively utilizing a so-called dissolution physical development action in a development reaction process. On the other hand, higher stability (preservation) of the developer is desired. If the developer is stable against air oxidation for a long time, constant photographic performance can be obtained without troublesome maintenance and management of the developer. In particular, when maintaining and managing the liquid composition while replenishing a fixed amount of replenisher with an automatic developing machine (hereinafter referred to as an automatic developing machine), both in terms of reducing the amount of replenisher and running costs. It is important. To reduce this replenisher volume, the developer stability must be higher. This is because the decrease in the amount of the replenisher further increases the residence time of the developer in the automatic developing machine and in the replenisher tank and increases the degree of air oxidation of the developer.

[0004] Air oxidation of a developer can be prevented by increasing the sulfite concentration in the developer, but there is a limit to increasing the sulfite concentration. One of the reasons is as follows. That is, usually, a concentrated solution obtained by concentrating a developing solution is prepared several times, and it is used by diluting it when actually performing development processing. One of the largest factors controlling the concentration of the concentrated solution is sulfite. . To increase the stability of the developer, the enrichment decreases when a large amount of sulfite is added.In extreme cases, the enrichment is the same from the time when the developer is first prepared to the time when it is used on-site on an automatic processor. That is, the same volume of developer is used, which is very disadvantageous in terms of transportation and space. Another reason is that a developer containing a large amount of sulfite increases the dissolution and elution of silver halide from the silver halide photosensitive material, resulting in more silver stains in the developer and contaminating the development rack and rollers. It is because it will be.

[0005] For these reasons, the amount of sulfite that is effective in improving the stability of the developer is increased, and there is no limit even if it is desired to include the sulfite in the developer.
In recent years, there has been an increasing demand for improved preservation. Ascorbic acid is known as a means for improving the preservability of a developer. As a known technique to be added to the squirrel developing solution, there is, for example, Japanese Patent Publication No. 44-28673. However, the disadvantages of ascorbic acid are that when the ascorbic acid is deteriorated, the pH of the developing solution is lowered, and the ascorbic acid is easily decomposed. It is mentioned that metal ions such as copper ions and iron ions are easily decomposed when present. The ascorbic acid derivative is a compound that has been known for a long time, and there are some other uses in the art. US Patent No. 26
In JP-A-88549 and JP-B-36-17599, it is used as a preservative for developing activity, gradation improvement, and 3-pyrazolidones. In fact, when this compound was evaluated, it had an excellent air oxidation suppressing function of the developer,
There is a problem that the developing activity is lowered because the pH of the developing solution is lowered.

[0006]

SUMMARY OF THE INVENTION Accordingly, a first object of the present invention is to improve the air oxidation stability of a developer containing hydroquinones as a developing agent. A second object is to increase the stability of the developer while maintaining the concentration of the developer concentrate. A third object is to increase the stability of the developer without promoting silver contamination. A fourth object is to increase the stability of the developer, thereby reducing the replenishment amount of the developer, reducing the pollution load, and improving the economics of the development processing.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to provide a method for developing an exposed silver halide photographic material using a developing solution containing dihydroxybenzenes.
The present invention has been attained by a method for processing a silver halide photographic material, wherein the developer is processed with a developer containing at least one compound represented by the following general formula (A). General formula (A)

[0008]

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In the formula, R ₁ and R ₂ each represent a hydroxy group, X is composed of a carbon atom or a nitrogen atom,
X forms a 5- to 6-membered ring in cooperation with the two vinyl carbons and the carbonyl carbons substituted by R ₁ and R ₂ .

[0010]

[0011]

Hereinafter, the general formula (A) will be described in detail. In the formula, R ₁ and R ₂ are each a hydroxy group, X is a carbon atom or a nitrogen atom, and X is a 5- to 6-membered member in cooperation with two vinyl carbons and a carbonyl carbon substituted by R ₁ and R _2. Construct a ring. As a specific example of X, -C
_{(R 5) (R 6)} -, - C (R 7) =, - C (= O)
_{-, - N (R 8)} -, - N =, constructed by combining. However, R ₅ , R ₆ , R ₇ , and R ₈ are a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may be substituted (a hydroxy group, a carboxy group, a sulfo group can be given as a substituent), and a carbon number. 6 to 15 optionally substituted aryl groups (substituents include an alkyl group, a halogen atom, a hydroxy group, a carboxy group and a sulfo group),
Represents a hydroxy group and a carboxy group. Further, a saturated or unsaturated condensed ring may be formed on the 5- or 6-membered ring.
Examples of the 5- to 6-membered ring include a cyclopentenone ring, a cyclohexenone ring, a pyrrolinone ring, a pyrazolinone ring, a pyridone ring, an azacyclohexenone ring, and a uracil ring. Examples thereof include a cyclopentenone ring, a cyclohexenone ring, a pyrazolinone ring, an azacyclohexenone ring, and a uracil ring.

[0013]

[0014]

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[0015]

[0016]

[0017]

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[0018]

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[0019]

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[0020]

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[0021]

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[0022]

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[0023]

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[0024]

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[0025]

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[0026]

[0027]

[0028]

[0029]

[0030]

[0031]

[0032]

[0033]

[0034]

The compound represented by the general formula (A) is described in US Pat. H
esse, Method der Organis
chen Chemie, vol. 4,217-29
8. D. R. Bender, J.M. Org. Chem. ,
vol. 40, 1264 (1975). US Pat. 4
128425. A. Stein, J.M. Am. Chem.
Soc. , Vol. 78, 6185 (1956). It can be synthesized according to a general synthesis method such as The amount of the compound represented by the general formula (A) is preferably 0.1 to 50 g, more preferably 0.5 to 2 g per liter of the developer.
5 g. The dihydroxybenzene-based developing agents used in the present invention include hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, methylhydroquinone, 2,3-dichlorohydroquinone, 2,5-dichlorohydroquinone, 2,3-dibromohydroquinone, 2,5 -Dimethylhydroquinone, hydroquinone monosulfonate and the like, but hydroquinone and hydroquinone monosulfonate are particularly preferred.

The p-aminophenol-based developing agents used in the present invention include N-methyl-p-aminophenol,
p-aminophenol, N- (β-hydroxyethyl)
-P-aminophenol, N- (4-hydroxyphenyl) glycine, 2-methyl-p-aminophenol, p
-Benzylaminophenol and the like, among which N-
Methyl-p-aminophenol is preferred. The 3-pyrazolidone-based developing agents used in the present invention include 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-methyl-4-
Hydroxymethyl-3-pyrazolidone, 1-phenyl-
4,4-dihydroxymethyl-3-pyrazolidone, 1-
Phenyl-5-methyl-3-pyrazolidone, 1-p-aminophenyl-4,4-dimethyl-3-pyrazolidone,
1-p-tolyl-4,4-dimethyl-3-pyrazolidone, 1-p-tolyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, and the like.

The dihydroxybenzene-based developing agent is used in an amount of usually 0.01 mol / l to 1.5 mol / l, preferably 0.05 mol / l to 1.2 mol / l. In addition to this, the p-aminophenol-based developing agent or 3-pyrazolidone-based developing agent is usually 0.0005 mol / L to 0.2 mol / L,
Preferably, it is used in an amount of 0.001 mol / l to 0.1 mol / l.

As the sulfite used in the developer of the present invention, sodium sulfite, potassium sulfite, lithium sulfite,
Ammonium sulfite, sodium bisulfite, potassium metabisulfite, and the like. The amount of sulfite is preferably 0.1 mol / liter or more. The upper limit is 2.
Preferably it is up to 5 mol / l. The pH of the developing solution used in the developing treatment of the present invention is preferably in the range of 9 to 13. More preferably, the pH is in the range of 9.3 to 12. The alkaline agent used for setting the pH includes a pH adjuster such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate tribasic, and potassium phosphate tribasic. JP-A-62-18
Buffers such as 6259 (borate), JP-A-60-93433 (for example, saccharose, acetoxime, 5-sulfosalicylic acid), phosphate and carbonate may be used.

In the present invention, the developer preferably contains a chelating agent having a chelate stability constant for iron ions of 8 or more. Here, the chelate stability constant is
L. G. FIG. Sillen A. E. FIG. .Martell, H "Stabillity
Constants of Metal-ion Complexes ”, The Chemical
Society, London (1964). S. Chaberek A.
E. FIG. Martell, "Organic Sequestering Agents",
Wiley (1959). Etc. means a constant generally known.

In the present invention, examples of the chelating agent having a chelating stability constant for iron ions of 8 or more include organic carboxylic acid chelating agents, organic phosphoric acid chelating agents, inorganic phosphoric acid chelating agents, polyhydroxy compounds and the like.
Here, the iron ion means ferric ion (Fe ³⁺ ).

In the present invention, specific examples of the chelating agent having a chelate stability constant of 8 or more with ferric ion include the following compounds, but are not limited thereto. That is, ethylenediamine diorthohydroxyphenylacetic acid, triethylenetetramine hexaacetic acid,
Diaminopropanetetraacetic acid, nitrilotriacetic acid, hydroxyethylethylenediaminetriacetic acid, dihydroxyethylglycine, ethylenediaminediacetic acid, ethylenediaminedipropionic acid, iminodiacetic acid, diethylenetriaminepentaacetic acid, hydroxyethyliminodiacetic acid, 1,3-diamino-2- Propanoltetraacetic acid, transcyclohexanediaminetetraacetic acid, ethylenediaminetetraacetic acid, glycol etherdiaminetetraacetic acid, ethylenediamine-N, N,
N'N'tetrakismethylenephosphonic acid, nitrilo-
N, N, N-trimethylenephosphonic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, 1,1-diphosphonoethane-2-carboxylic acid, 2-phosphonobutane-1,
2,4-tricarboxylic acid, 1-hydroxy-1-phosphonopropane-1,2,3-tricarboxylic acid, catechol-3,5-disulfonic acid, sodium pyrophosphate, sodium tetrapolyphosphate, and sodium hexametaphosphate. .

The developer may be a dialdehyde hardener or a bisulfite adduct thereof. Specific examples thereof include glutaraldehyde and bisulfite adducts. Additives other than the above-mentioned components include development inhibitors such as sodium bromide, potassium bromide and potassium iodide: ethylene glycol, diethylene glycol, triethylene glycol, dimethylformamide, methyl cellosolve, hexylene glycol,
Organic solvents such as ethanol and methanol: mercapto compounds such as 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzimidazole-5-sulfonic acid sodium salt, indazole compounds such as 5-nitroindazole, 5-methylbenztriazole Antifoggants such as benztriazole-based compounds such as those described in Research Disclosure Vol. 176, No. 1764
3. It may contain the development accelerator described in Section XXI (December issue, 1978) and, if necessary, a color tone agent, a surfactant, an antifoaming agent, a water softener and the like.

In the developing treatment of the present invention, a silver stain inhibitor other than the silver stain inhibitor of the present invention is added to the developing solution, for example, as disclosed in
The compounds described in JP-A-6-24347 can be used. The developer of the present invention includes European Patent Publication 1365.
No. 82, UK Patent No. 958678, US Patent No. 323
Amino compounds such as alkanolamines described in U.S. Pat. No. 2,761 and JP-A-56-106244 can be used for the purpose of accelerating development, increasing contrast and other purposes. In addition, L. F. A. Mason, Photographic Processing Chemistry, Focal Press (19
66), pages 226-229, U.S. Pat.
Nos. 015 and 2,592,364, JP-A-48-64.
933 or the like may be used.

The fixing solution is an aqueous solution containing thiosulfate.
It has a pH of 3.8 or more, preferably 4.2 to 7.0.
Examples of the fixing agent include sodium thiosulfate and ammonium thiosulfate, and ammonium thiosulfate is particularly preferable from the viewpoint of fixing speed. The amount of the fixing agent to be used can be appropriately changed, and is generally about 0.1 to about 6 mol / liter. The fixing solution may contain a water-soluble aluminum salt acting as a hardener, and examples thereof include aluminum chloride, aluminum sulfate, potassium alum and the like. Here, the amount of the water-soluble aluminum salt is usually 0.4 to 2.
0 g-Al / liter. Further, a trivalent iron compound can be used as an oxidizing agent as a complex with ethylenediaminetetraacetic acid. The fixing solution contains tartaric acid, citric acid, gluconic acid or a derivative thereof alone or
More than one species can be used in combination. It is effective that these compounds contain 0.005 mol or more per liter of the fixing solution, and particularly 0.01 to 0.03 mol / l is particularly effective. The fixing solution may optionally contain a preservative (for example, sulfite or bisulfite), a pH buffer (for example, acetic acid or boric acid), a pH adjuster (for example, sulfuric acid), a chelating agent having a water softening property, Compounds described in JP-A-62-78551 can be included.

In the present invention, the term "development step time" or "development time" refers to the time from the time when the tip of the photosensitive material to be processed is immersed in the developing tank solution of the automatic developing machine to the time when it is immersed in the next fixing solution. The “fixing time” is the time from immersion in the fixing tank solution to immersion in the next washing tank solution (stabilizing solution). “Washing time” refers to the time of immersion in the washing tank solution. The “drying time” is usually 35 ° C. to 100 ° C.
A drying zone to which hot air of preferably 40 ° C. to 80 ° C. is blown is installed, and it refers to a time in the drying zone. In the development processing of the present invention, the development time is 5 seconds to 1 minute, preferably 5 seconds to 30 seconds, and the development temperature is 25 seconds.
C. to 50.degree. C. are preferred, and 25.degree. Fixing temperature and time are about 20 ° C to about 50 ° C for 5 seconds to 1
Minutes is preferable, and 5 seconds to 30 seconds at 25 ° C to 40 ° C is more preferable. The temperature and time of the washing or stabilizing bath are preferably 5 seconds to 1 minute at 0 to 50 ° C, and 5 seconds to 30 minutes at 15 ° C to 40 ° C.
Seconds are more preferred.

According to the method of the present invention, the photographic material which has been developed, fixed and washed (or stabilized) is squeezed out of the washing water, ie, dried through a squeeze roller. Drying is carried out at about 40 ° C. to about 100 ° C., and the drying time can be appropriately changed depending on the surrounding conditions, but it is usually about 5 seconds to 1 minute, particularly preferably 40 ° C. to 80 ° C. for about 5 seconds. ~
30 seconds.

The photographic light-sensitive material to which the method for developing a light-sensitive material of the present invention is applied is not particularly limited. In addition to a general black-and-white light-sensitive material, a color light-sensitive material to be subjected to reversal processing (for example, a color reversal film or paper) Can also be used. In particular, photographic photosensitive materials for laser printers and photographic materials for medical images, as well as medical direct imaging X-ray photographic materials, medical indirect imaging X-ray photographic materials, hydrazine nucleation-based high contrast films, CRT image recording photographic materials, It is preferably used for micro-sensitive materials, general black-and-white negative films, black-and-white printing paper, and the like.

The halogen composition of the silver halide emulsion used in the present invention is not particularly limited, and examples thereof include silver chloride, silver iodide, silver bromide, silver chlorobromide, silver iodobromide, and silver chloroiodobromide. Silver halide dispersed in a hydrophilic colloid. Silver halide emulsions are usually prepared by methods well known in the art (eg,
A water-soluble silver salt (eg, silver nitrate) and a water-soluble halogen salt are mixed in the presence of water and a hydrophilic colloid by a single jet method, a double jet method, a control jet method, and the like, and subjected to physical ripening and gold sensitization and / or gold sensitization. Alternatively, it is produced through chemical ripening such as sulfur sensitization. There are no particular restrictions on the grain shape of the silver halide used in the present invention, and in addition to cubic, octahedral, and spherical shapes, Research Disclosure
Any of the tabular silver halide grains having a high aspect ratio described in 22534 (January 1983) can be used.

In the case of an X-ray photographic material, it is preferable to use a tabular silver halide emulsion. In this case, silver bromide or silver iodobromide is preferred.
-5 mol% is preferred, and a highly sensitive one is obtained, and it is suitable for rapid processing. The tabular silver halide emulsion preferably has an aspect ratio of from 4 to less than 20, more preferably from 5 to less than 10. Further, the thickness of the particles is preferably 0.3 μm or less, particularly preferably 0.2 μm or less. Here, the aspect ratio of the tabular silver halide emulsion is given by the ratio of the average value of the diameter of a circle having an area equal to the projected area of each tabular grain to the average value of the thickness of each tabular grain. . The tabular grains are preferably present in an amount of preferably 80% by weight, more preferably 90% by weight or more of all grains in the tabular silver halide emulsion. By using a tabular silver halide emulsion, the photographic stability during running processing according to the present invention can be further enhanced. Further, since the amount of coated silver can be reduced, the load on the fixing step and the drying step is particularly reduced, and rapid processing can be performed from this point as well.

The tabular silver halide emulsion was prepared from Knack (Cu
gnac) and Chateau, "Evolution of Morphology of Silver Bromide Crystals during Physical Ripening (Evolution of the Morphology of Silver Promide Crystals Dualing Physical Ripping)" Science・ E-Industrie Photography, 3
3, No.2 (1962), pp. 121-125, Duffin, Photographic emulsion chemistry
Focal Press, New York, 1966, p. 66 to p. 72, APH Tribvlli, WF Smith, Photographic Journal, 80, 28
5 (1940), etc.
127, 921, JP-A-58-113,927, JP-A-58-113,928, etc., and can be easily prepared.

Also, in an atmosphere having a relatively pBr value of pBr 1.3 or less, a seed crystal in which tabular grains are present in an amount of 40% or more by weight is formed, and silver and a halogen solution are added simultaneously while maintaining the same pBr value. While growing a seed crystal. It is desirable to add a silver and halogen solution so that no new crystal nuclei are generated during the grain growth process. The size of the tabular silver halide grains can be adjusted by controlling the temperature, selecting the type and amount of the solvent, and using a silver salt for growing the grains.
And the rate of addition of the halide can be controlled.

The silver halide emulsion used in the present invention may be a polydisperse emulsion or a monodisperse emulsion having a uniform particle size distribution. In particular, the photographic material for printing has a dispersion coefficient of 2 representing the particle size distribution.
Monodispersed emulsions of 0% or less are preferred. Here, the monodisperse emulsion means a silver halide emulsion having a grain size distribution having a coefficient of variation of 20% or less, particularly preferably 15% or less. Here, the coefficient of variation is the coefficient of variation (%) = (standard deviation of particle size / average value of particle size) ×
100.

In the silver halide grains, the inside and the surface layer may be composed of a uniform phase or may be composed of different phases. Two or more kinds of silver halide emulsions formed separately may be used as a mixture. Further, the latent image may be a particle mainly formed on the surface of the particle, or a particle mainly formed inside the particle. Further, the particles may be particles whose surface is previously covered.

The silver halide emulsion used in the present invention contains a cadmium salt, a sulfite, a lead salt, a thallium salt, a rhodium salt or a complex salt thereof, an iridium salt or a complex salt thereof during the formation of silver halide grains or physical ripening. They may coexist. In particular, when the purpose is to enhance the contrast and to improve the reciprocity failure property, 10 ^-8 to 10 ^-8 mol per mol of silver halide is required.
It is preferred to prepare silver halide in the presence of 10 ^-3 moles of the iridium salt. The silver halide emulsion of the present invention may be an emulsion containing at least one of iron, rhenium, ruthenium and osmium compounds. Addition amount is silver 1
10 ^-3 mol or less, preferably 10 ^-6 mol, per mol.
10 to 10 ^-4 mol.

The emulsion of the present invention may not be chemically sensitized, but may be. As the method of chemical sensitization, known methods such as sulfur sensitization, reduction sensitization, and gold sensitization can be used, and they are used alone or in combination. The preferred chemical sensitization method is sulfur sensitization. As a sulfur sensitizer, in addition to sulfur compounds contained in gelatin,
Various sulfur compounds such as thiosulfates, thioureas, thiazoles, rhodanines and the like can be used. Specific examples are described in U.S. Pat. Nos. 1,574,944 and 2,278,
947, 2,410,689, 2,728,6
No. 68, No. 3, 501, 313, No. 3, 656, 95
No.5. Preferred sulfur compounds are
Thiosulfate, thiourea compound, pA during chemical sensitization
g is preferably 8.3 or less, more preferably
It is in the range of 7.3 to 8.0. Moisar, Klein G
elatione. Proc. Symp. 2nd, 301-309 (197
0) et al. Also use polyvinylpyrrolidone and thiosulfate in combination to give good results.

The gold sensitization method is a typical one of the noble metal sensitization methods, and uses a gold compound, mainly a gold complex salt. Noble metals other than gold, for example, complex salts such as platinum, palladium and iridium may be contained. An example is U.S. Pat.
448,060 and British Patent 618,061. Also, a sulfur sensitization method using a sulfur-containing compound, a Se sensitization method using a Se sensitizer, a Te sensitization method using a Te sensitizer, a reduction sensitization method using a complex salt, a polyamine, or the like, More than one combination can be used. Examples of the reduction sensitizer include stannous salts, amines, sulfinoformamidine, dialkylaminoborane, and silane compounds. Specific examples thereof are described in U.S. Pat. Nos. 2,487,850 and 2,518, 6
No. 98, 2,983,609, 2,983,610
No. 2,694,637.

The swelling percentage referred to in the present invention is determined by (a) incubating the photographic material at 38 ° C. and 50% relative humidity for 3 days, (b) measuring the thickness of the hydrophilic colloid layer,
(C) immersing the photographic material in distilled water at 21 ° C. for 3 minutes and (d) measuring the percentage change in layer thickness compared to the thickness of the hydrophilic colloid layer measured in step (b) Can be obtained by: In the present invention, the hydrophilic colloid layer containing at least one silver halide emulsion layer has a swelling percentage of 250 or less, and preferably a swelling percentage of 230% or less and 170% or more.

Such rapid processing and simplification of the processing are better achieved by further reducing the swelling percentage. On the other hand, if the percentage of swelling is reduced, the speed of development, fixing, washing with water and the like is reduced.

Examples of usable hardening agents include aldehyde compounds, compounds having an active halogen described in US Pat. No. 3,288,775, and US Pat.
No. 3,091,537, compounds having a reactive ethylenically unsaturated group described in US Pat.
And organic compounds such as halogenocarboxaldehydes such as mucochloric acid. Among them, vinyl sulfone hardeners are preferred. Further, a polymer hardener can be preferably used in the present invention.

As the polymer hardener used in the present invention, a polymer having an active vinyl group or a group which is a precursor thereof is preferable. Among them, a long spacer as described in JP-A-56-142524 is preferable. Particularly preferred are polymers in which the active vinyl group or its precursor group is bonded to the polymer main chain. The amount of these hardeners to achieve the swelling percentage of the present invention varies depending on the type of hardener used and the kind of gelatin used.

The silver halide grains used in the present invention are preferably spectrally sensitized with a sensitizing dye. The dyes used include cyanine dyes, merocyanine dyes,
Complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes are included. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes. Any of the nuclei usually used for cyanine dyes as base heterocyclic nuclei can be applied to these dyes. That is, a pyrroline nucleus, an oxazoline nucleus, a thiazoline nucleus, a pyrrole nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus, an imidazole nucleus, a tetrazole nucleus, a pyridine nucleus, and the like; a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; A nucleus in which an aromatic hydrocarbon ring is fused to the nucleus of, i.e., indolenine nucleus, benzoindolenine nucleus, indole nucleus, benzoxadol nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benzo An imidazole nucleus, a quinoline nucleus and the like can be applied. These nuclei may be substituted on carbon atoms.

In the merocyanine dye or the complex merocyanine dye, pyrazolin-5-one nucleus, thiohydantoin nucleus, 2-thiooxazolidine-2,4-dione nucleus, thiazolidine-2,4-dione nucleus and rhodanine as nuclei having a ketomethylene structure. 5 such as nucleus and thiobarbituric acid nucleus
A 6-membered heterocyclic nucleus can be applied. In particular,
Research Disclosure Volume 170 RD-1764
3 (December 1978), p. 23, U.S. Pat.
Nos. 5,425 and 4,425,426, specifically, the following compounds can be used.

5,5'-dichloro-3,3'-diethylthiocyanine bromide, 5,5'-dichloro-3,3'-
Di (4-sulfobutyl) -thiocyanine Na salt, 5-methoxy 4,5-benzo-3,3'-di (3-sulfopropyl) thiocyanine Na salt, 5,5'-dichloro-3,
3'-diethyl selenocyanine iodide 5,5'-dichloro-9-ethyl-3,3'-di (3-
Sulfopropyl) thiacarbocyanine pyridinium salt,
Anhydro-5,5'-dichloro-9-ethyl-3-
(4-sulfobutyl) -3'-ethyl hydroxide, 1,1
-Diethyl-2,2'-cyanine bromide, 1,1-dipentyl-2,2'-cyanine perchlorate, 9-methyl-
3,3'-di (4-sulfobutyl) -thiacarbocyanine pyridinium salt, 5,5'-diphenyl-9-ethyl-3,3'-di (2-sulfoethyl) -oxacarbocyanine Na salt, 5-chloro -5'-phenyl-9-ethyl-3- (3-sulfopropyl) -3 '-(2-sulfoethyl) oxacarbocyanine Na salt, 5,5'-dichloro-9-ethyl-3,3'-di (3-Sulfopropyl) oxacarbocyanine Na salt, 5,5'-dichloro-6,6'-dichloro-1,1'-diethyl-3,3 '
-Di (3-sulfopropyl) imidacarbocyanine Na
Salt, 5,5'-diphenyl-9-ethyl-3,3'-di (3-sulfopropyl) thiacarbocyanine Na salt,

The sensitizing dye to be used in the present invention is generally added to the emulsion before the emulsion is coated on a suitable support. However, the sensitizing dye may be added during the chemical ripening step or the silver halide grain forming step. Good. The emulsion layer of the photographic light-sensitive material of the present invention can contain a plasticizer such as a polymer or an emulsion such as an alkyl acrylate latex or a polyol such as trimethylolpropane in order to improve pressure characteristics.

In the photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material prepared by using the present invention, coating aids, antistatic, improving slipperiness, emulsifying and dispersing, preventing adhesion and improving photographic properties (for example, development acceleration) For various purposes such as contrast enhancement, sensitization, and the like, various surfactants may be contained. For example, saponins (steroids), alkylene oxide derivatives (eg, polyethylene glycol, polyethylene glycol /
Polypropylene glycol condensates, polyethylene glycol alkyl ethers or polyethylene glycol alkyl aryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycol alkylamines or amides, polyethylene oxide adducts of silicone), glycidol derivatives ( Nonionic surfactants such as alkenyl succinic acid polyglyceride, alkylphenol polyglyceride), fatty acid esters of polyhydric alcohols, alkyl esters of sugars, etc .; alkyl carboxylate, alkyl sulfonate, alkyl benzene sulfonate, alkyl Naphthalene sulfonates, alkyl sulfates, alkyl phosphates, N-acyl-N-alkyl Such as taurine, sulfosuccinates, sulfoalkyl polyoxyethylene alkyl phenyl ethers, polyoxyethylene alkyl phosphates, carboxy group, sulfo group, phospho group, sulfate group, phosphate group, etc. Anionic surfactants containing an acidic group; amphoteric surfactants such as amino acids, aminoalkyl sulfonic acids, aminoalkyl sulfates or phosphates, alkyl betaines, amino oxides; alkylamine salts, aliphatic or aromatic Quaternary ammonium salts, pyridinium,
Heterocyclic quaternary ammonium salts such as imidazolium,
And cationic surfactants such as phosphonium or sulfonium salts containing aliphatic or heterocyclic rings.

The halogen surfactant photographic light-sensitive material used in the present invention has at least one emulsion layer of a halogen surfactant on a support. 58-127921, 59-908
No. 41, No. 58-111934, No. 61-20123
As described in No. 5, etc., those having at least one silver halide emulsion layer on each side of the support are preferred. The photographic material of the present invention may further have an intermediate layer, a filter layer, an antihalation layer, and the like, if necessary. The silver content of the light-sensitive material used in the present invention is preferably 0.5 g / m ^{2 to} 5 g / m ² (on one side), and more preferably 1 g / m ^{2 to} 3 g / m ² (on one side). Preferably, the suitability for rapid processing does not exceed 5 g / m ² . Further, in order to obtain a constant image density and a constant contrast, 0.5 g / m ² or more is preferable.

As a binder or protective colloid of a photographic emulsion, gelatin is advantageously used, but other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, albumin, protein hydroxyethylcellulose such as casein, carboxymethylcellulose, cellulose derivatives such as cellulose sulfates, sodium alginate, sugar derivatives such as starch derivatives, polyvinyl alcohol, Polyvinyl alcohol partial acetal, poly-N
-Various kinds of synthetic hydrophilic high-molecular substances such as homo- or copolymers such as vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole and polyvinylpyrazole can be used. As gelatin, in addition to lime-processed gelatin, acid-processed gelatin may be used, and gelatin hydrolyzate and gelatin enzyme hydrolyzate can also be used.

It is particularly preferable for the X-ray sensitive material to include an organic substance which can be discharged in the development processing step in the emulsion layer or in the hydrophilic colloid layer. When the substance to be washed away is gelatin, a gelatin species which is not involved in the crosslinking reaction of gelatin by the hardener is preferable, for example, acetylated gelatin or phthalated gelatin, and a material having a small molecular weight is preferable. On the other hand, as a polymer substance other than gelatin, US Pat. No. 3,271,1
Polyacrylamide as described in No. 58, or alternatively, polyvinyl alcohol, a hydrophilic polymer such as polyvinylpyrrolidone can be effectively used,
Sugars such as dextran, saccharose and pullulan are also effective. Among them, polyacrylamide and dextran are preferable, and polyacrylamide is a particularly preferable substance. The average molecular weight of these substances is preferably 20,000 or less, more preferably 10,000 or less. The amount of the effluent in the processing is preferably 10% or more and 50% or less of the total weight of the coated organic substance other than the silver halide grains, and is preferably 15% or less.
% Or more and preferably 30% or less. The layer containing the organic substance flowing out in the treatment of the present invention may be either an emulsion layer or a surface protective layer.However, when the total amount of the organic substance applied is the same, the layer containing the organic substance is more effective than the layer containing only the emulsion layer. It is preferable that the compound is contained in the emulsion layer, and it is more preferable that the compound is contained only in the surface protective layer. In the case of a light-sensitive material in which the emulsion layer has a multilayer structure, when the total coating amount of the organic substance is the same,
It is preferable that a larger amount be contained in the emulsion layer closer to the surface protective layer.

As the antistatic agent, in particular, JP-A-62-1
Fluorine-containing surfactants or polymers described in JP-A-09-9444 and JP-A-62-215272;
No. 60-80846, No. 60-80848, 6
Nos. 0-80839, 60-76741, 58-2
No. 08743, No. 62-172343, No. 62-17
Nonionic surfactants described in JP-A Nos. 3459 and 62-215272, and JP-A-57-15772.
Conductive polymers or latexes (nonionic, anionic, cationic, amphoteric) described in JP-A Nos. 204540 and 62-215272 can be preferably used. As the inorganic antistatic agent, conductive tin oxide and zinc oxide described in JP-A-57-118242 and composite oxides of these metal oxides doped with antimony or the like can be preferably used.

It is particularly preferable to use a fluorine surfactant as the antistatic agent. In the present invention, it is preferable to include an organic substance which flows out in the development step in the emulsion layer and / or the other hydrophilic colloid layer. When the substance to be discharged is gelatin, a gelatin species which is not involved in the cross-linking reaction of gelatin by a hardener is preferable. For example, acetylated gelatin and phthalated gelatin correspond to these, and those having a small molecular weight are preferable. On the other hand, as a polymer substance other than gelatin, U.S. Pat.
No. 271,158, polyacrylamide, or a hydrophilic polymer such as polyvinyl alcohol and polyvinylpyrrolidone can be used effectively, and dextran, saccharose, bullran and the like are also effective. Among them, polyacrylamide and dextran are preferable, and polyacrylamide is a particularly preferable substance. The average molecular weight of these substances is preferably 20,000 or less, more preferably 10,000 or less. It is effective that the amount of the effluent in the processing is 10% or more and 50% or less of the total weight of the coated organic substance of silver halide grains or less.

In the present invention, US Pat. Nos. 2,929,101, 2,701,245 and 41,428 as matting agents are used.
No. 94, No. 4,396,706 Use of homopolymers of polymethyl methacrylate or copolymers of methyl methacrylate and methacrylic acid, organic compounds such as starch, and fine particles of inorganic compounds such as silica, titanium dioxide, sulfuric acid and strontium barium as described in JP-A Nos. 94 and 4396706. Can be.
The particle size is 1.0 to 10 μm, particularly 2 to 5 μm
It is preferred that

The silver halide photographic light-sensitive material of the present invention has a purpose of absorbing light in a specific wavelength range, that is, performing halation or irradiation, or providing a filter layer to adjust the spectral composition of light to be incident on the photographic emulsion layer. The photographic emulsion layer or other layers may be colored with a dye for control or the like. In a double-sided film such as a direct medical x-ray film, a layer for crossover cut may be provided below the emulsion layer. Such dyes include oxonol dyes having a pyrazolone nucleus or barbituric acid nucleus, azo dyes, azomethine dyes, anthraquinone dyes,
Examples include arylidene dyes, styryl dyes, triarylmethane dyes, merocyanine dyes, and cyanine dyes.

When these dyes are used, it is an effective technique to mordant an anionic dye to a specific layer in a light-sensitive material using a polymer having a cation site. In this case, it is preferable to use a dye which irreversibly decolorizes during the development-fixing-washing step. The layer in which the dye is mordanted by using a polymer having a cation site may be the emulsion layer, the surface protective layer may be on the side opposite to the emulsion layer and the support, but preferably between the emulsion layer and the support. For the purpose of crossover cutting of medical X-ray double-sided films, it is ideal to mordant into the undercoat layer. As a coating aid for the undercoat layer, a polyethylene oxide-based nonionic surfactant can be preferably used in combination with a polymer having a cation site. As the polymer providing the cation site, an anion conversion polymer is preferable.

As the anion conversion polymer, various known quaternary ammonium salt (or phosphonium salt) polymers can be used. Quaternary ammonium salt (or phosphonium salt)
The polymer is widely known as a mordant polymer or an antistatic polymer in the following publications and the like. JP 5
9-166,940; U.S. Pat. No. 3,958,995;
JP-A-55-142339, JP-A-54-126,02
7, JP-A-54-155835, JP-A-53-303
28. Water-dispersed latex described in JP-A-54-92274; U.S. Pat. Nos. 2,548,564 and 3,1.
48,061 and 3,756,814; polyvinylpyridinium salts; water-soluble quaternary ammonium salt polymers described in U.S. Pat. No. 3,709,690; and water-insoluble quaternary ammonium salts described in U.S. Pat. And quaternary ammonium salt polymers. Further, a monomer having at least two (preferably 2 to 4) ethylenically unsaturated groups is copolymerized because it moves from the desired layer to another layer or into the processing solution and does not have a photographically unfavorable effect. It is particularly preferable to use a crosslinked aqueous polymer latex. As a method for immobilizing a dye, see
The solid dispersion method described in 5-155350 and WO88 / 04794 is also effective.

The light-sensitive material used in the present invention may be one which is designed to exhibit ultra-high contrast photographic characteristics using a hydrazine nucleating agent. This system and the hydrazine nucleating agent used are described in the following documents. This system is particularly preferably used for graphic arts. RESEARCH DISCLOSURE Item 23516 (19
November 1983, p. 346) and references cited therein, U.S. Pat. Nos. 4,080,207 and 4,26.
9,929, 4,276,364, 4,27
8,748, 4,385,108, 4,45
9,347, 4,560,638, 4,47
No. 8,928, British Patent 2,011,391B, JP-A-60-179834, JP-A-62-270,948, JP-A-63-29,751, JP-A-61-170,733.
No. 61-270,744, No. 62-948, E
P217,310, JP-A-63-32538, 6
3-104,047, 63-121,838, 63-129,337, 63-234,245,
63-234,246, 63-223,744
Nos. 63-294,552 and 63-306,43
No. 8, No. 64-10,233 or US 4,68
No. 6,167, JP-A-62-178,246, 63-63
JP-A-234,244, JP-A-64-90,439, JP-A-1-276,128, JP-A-1-283,548, JP-A-1
-280,747, 1-283549, 1-2
No. 85,940, No. 2-2541, No. 2-139,5
No. 38, No. 2-177,057, No. 2-198, 44
No. 0, 2-198, 441, 2-198, 442
Nos. 2-196, 234 and 2-196, 235
No. 2-220,042, 2-221, 953
No. 2-221, 954 and the like.

When a hydrazine nucleating agent is contained in a photographic light-sensitive material, it is preferably contained in a silver halide emulsion layer, but other non-light-sensitive hydrophilic colloid layers (for example, a protective layer, an intermediate layer, a filter layer) , An antihalation layer, etc.). The amount of the hydrazine nucleating agent to be added is from 1 × 10 ^-6 mol to 5 × 10 ⁶ per mol of silver halide.
^-2 mol is preferable, and in particular, 1 × 10 ^-5 mol to 2 × 1
A range of 0 ^-2 mol is preferred.

Examples of development accelerators suitable for use in this ultra-high contrast system or accelerators for nucleation and infectious development include JP-A-53-77616, JP-A-54-37732, and JP-A-53-173.
37,133, 60-140,340, 60-14
959, and various compounds containing an N or S atom are effective. The optimum amount of these accelerators varies depending on the type of the compound.
× 10 ^{−3 to} 0.5 g / m ² , preferably 5.0 × 10 ⁻³ to
It is desirable to use in the range of 0.1 g / m ² .

Further, in a super-high contrast system, a redox compound which releases a development inhibitor can be used in combination. As this redox compound, JP-A-2-293
736, 2-308, 239, JP-A-1-154
No. 060, No. 1-205885 and the like. Its use amount is from 1 × 10 ^{−6 to} 5 × 10 ⁻² mol, especially from 1 × 10 ⁻⁵ mol per mol of silver halide.
It is preferable to use it in the range of 1 × 10 ^-2 mol.

The light-sensitive material of the present invention can contain various compounds for the purpose of preventing fog during the production process, storage or photographic processing of the light-sensitive material or stabilizing photographic performance. That is, azoles such as benzothiazolium salts, nitroindazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptotetrazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptothiadiazoles, aminotriazoles, benzothiazoles, nitro Benzotriazoles, etc .; mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxazolinethione; azaindenes such as triazaindenes, tetraazaidenes (especially 4-
Hydroxy-substituted (1,3,3a, 7) tetraazaindenes, pentaazaindenes and the like; known as antifoggants or stabilizers such as benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonamide and the like. Many compounds can be added. Among these, preferably benzotriazole (for example, 5
-Methyl-benzotriazole) and nitroindazoles (eg, 5-nitroindazole). Also,
These compounds may be contained in the processing solution. Further, a compound capable of releasing an inhibitor during the development described in JP-A-62-30243 can be contained for the purpose of stabilizing or preventing black spots.

The photographic light-sensitive material of the present invention may contain a developing agent such as a hydroquinone derivative or a phenidone derivative for various purposes such as a stabilizer and an accelerator. The photographic light-sensitive material of the present invention may contain an inorganic or organic hardener in the photographic emulsion layer and other hydrophilic colloid layers. For example, chromium salts (chromium alum, chromium acetate, etc.), aldehydes (formaldehyde, glutaraldehyde, etc.), N-methylol compounds (dimethylolurea, etc.), dioxane derivatives, active vinyl compounds (1,3,3
5-triacryloyl-hexahydro-s-triazine, 1,3-vinylsulfonyl-2-propanol, etc., active halogen compounds (2,4-dichloro-6-hydroxy-s-triazine, etc.), mucohalic acids (mucochloric acid) And the like can be used alone or in combination.

The photographic light-sensitive material of the present invention contains a hydroquinone derivative (so-called DIR-hydroquinone) which releases a development inhibitor in a photographic emulsion layer or another hydrophilic colloid layer in accordance with the density of an image during development. You may. Specific examples thereof are described in U.S. Pat. No. 3,379,529, U.S. Pat. No. 3,620,746, and U.S. Pat.
No. 634, U.S. Pat. No. 4,332,878,
9-129,536, JP-A-54-67,419,
JP-A-56-153,336, JP-A-56-153,
No. 342, JP-A-59-278853, and JP-A-59-9.
Nos. 0435, 59-90436, 59-1388
No. 08 and the like.

The light-sensitive material used in the present invention may contain a dispersion of a water-insoluble or hardly soluble synthetic polymer for the purpose of dimensional stability. For example, use is made of a polymer having, as a monomer component, an alkyl (meth) acrylate, an alkoxyacryl (meth) acrylate, a glycidyl (meth) acrylate, or the like alone or in combination, or a combination thereof with acrylic acid, methacrylic acid, or the like. be able to.

The silver halide emulsion layer and other layers of the photographic light-sensitive material of the present invention preferably contain a compound having an acid group. Examples of the compound having an acid group include salicylic acid, acetic acid, organic acids such as ascorbic acid and acrylic acid,
A polymer or copolymer having an acid monomer such as maleic acid or phthalic acid as a repeating unit can be given. These compounds are disclosed in JP-A-61-2238.
No. 34, No. 61-228443, No. 62-25745
And the records of JP-B-62-55642 can be referred to. Particularly preferred among these compounds is ascorbic acid as the low molecular weight compound,
The polymer compound is a water-dispersible latex of a copolymer comprising an acid monomer such as acrylic acid and a crosslinkable monomer having two or more unsaturated groups such as divinylbenzene.

The silver halide emulsion thus produced is coated and dried on a support such as a cellulose acetate film or a polyethylene terephthalate film by a dipping method, an air knife method, a bead method, an extrusion doctor method, a double-side coating method or the like. You.

The present invention can also be used for color light-sensitive materials. In this case, various color couplers can be used. Here, the color coupler refers to a compound capable of forming a dye by a coupling reaction with an oxidized aromatic primary amine developing agent. Typical examples of useful color couplers include naphthol or phenolic compounds, pyrazolone or pyrazoloazole compounds, and open-chain or heterocyclic ketomethylene compounds. Specific examples of these cyan, magenta and yellow couplers that can be used in the present invention are Research Disclosure (RD) 17
643 (December 1978), Sections VII-D and 187
17 (November 1979). Various photographic additives that can be used in the present invention are described, for example, in Research Disclosure No. 1764, supra.
No. 3, pages 23-28 and No. 18716, 648-6.
It is described on page 51. The types of these additives and the places where they are described in detail are shown below.

Additive type RD17643 RD18716 1 Chemical sensitizer page 23, page 648, right column 2 Sensitivity enhancer Same as above 3 Spectral sensitizer, page 23-24, page 648 right column to supersensitizer 649, right column 4 Brightener page 24 5 Antifoggant page 24-25 page 649 right column and stabilizer 6 light absorber, ph 25-26 page 649 right column to filter dye 650 page left column Ultraviolet absorber 7 stain inhibitor page 25 Right column, page 650, left to right column 8 Dye image stabilizer, page 25 9 Hardener, page 26, page 651, left column 10 Binder, page 26 Same as above

[0087]

The present invention will be specifically described below with reference to examples.

Example 1 (Preparation of Emulsion) Preparation of Emulsion A 1 solution Water 1.0 l Gelatin 20 g Sodium chloride 20 g 1,3-Dimethylimidazolidin-2-thione 20 mg Sodium benzenethiosulfonate 8 mg 2 solutions Water 400 ml Silver nitrate 100 g 3 liquid water 400 ml sodium chloride 27.1 g potassium bromide 21 g potassium hexachloroiridium (III) acidate (0.001% aqueous solution) 15 ml ammonium hexabromorhodium (III) acidate (0.001% aqueous solution) 1.5 ml 38 ° C, pH 4.5 While stirring the second solution and the third solution to one solution to be dripped, simultaneously add over 10 minutes,
m of core particles were formed. Subsequently, the following liquids 4 and 5 were added over 10 minutes. 0.15g of potassium iodide
Was added to terminate the particle formation. Fourth liquid 400 ml Silver nitrate 100 g Five liquid 400 ml Sodium chloride 27.1 g Potassium bromide 21 g Potassium hexacyanoferrate (III) (0.1% aqueous solution) 5 ml After that, water was washed by flocculation according to a conventional method, and 30 g of gelatin was added. .

The pH and pAg were adjusted to 5.3 and 7.5, respectively.
2.6 mg of sodium thiosulfate, 1.0 mg of triphenylphosphine selenide and 6.2 mg of chloroauric acid were added, 4 mg of sodium benzenethiosulfonate and 1 mg of sodium benzenesulfinate were added, and the optimum sensitivity was obtained at 55 ° C. Chemical sensitization. 200 mg of 4-hydroxy-6-methyl-1,3,3a, 7-tetraazaindene was added as a stabilizer, and phenoxyethanol was added as a preservative. Finally, a silver iodochlorobromide cubic grain emulsion containing 70 mol% of silver chloride and having an average grain size of 0.2 μm was obtained. (Variation coefficient 9%)

(Preparation of Coated Sample) Ortho-sensitizing dye (the following compound) was added to the above emulsion at 5.times.10@-4 mol / mol Ag to perform ortho-sensitization. Hydroquinone, 1-phenyl-5-mercaptotetrazole as an antifoggant is Ag
2.5 g, 50 mg per mole, polyethyl acrylate latex as a plasticizer, 25% gelatin binder ratio, 2-bis (vinylsulfonylacetamide) ethane as a hardening agent, and colloidal silica at 40% gelatin binder ratio. and, Ag3.0g / m ² on a polyester support was coated so as to gelatin 1.0 g / m ^2. A lower protective layer and an upper protective layer having the following composition were simultaneously coated thereon.

[0091]

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<Lower Layer of Protective Layer> Gelatin 0.25 g / m ² Sodium benzenethiosulfonate 4 mg / m ² 1,5-dihydroxy-2-benzaldoxime 25 mg / m ² Polyethyl acrylate latex 125 mg / m ²

<Top layer of protective layer> Gelatin 0.25 g / m ² Silica matting agent having an average of 2.5 μm 50 mg / m ² Compound-1 (gelatin dispersion) 30 mg / m ² Colloidal silica having a particle size of 10 to ²⁰ μm 30 mg / m ² Compound-2 5 mg / m ² Sodium dodecylbenzenesulfonate 22 mg / m ²

[0094]

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The base used in this example has a back layer and a back protective layer having the following compositions. Sodium dodecylbenzenesulfonate 80 mg / m ² Compound -3 70 mg / m ² Compound -4 85 mg / m ² Compound -5 90mg / m ² 1,3- divinyl sulfone-2-propanol 60 mg / m ²

[0096]

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[0097] [Back protective layer] Gelatin 0.5 g / m ² Polymethyl methacrylate (particle size 4.7 [mu] m) of sodium 30 mg / m ² dodecylbenzenesulfonate 20 mg / m ² the compound -2 2 mg / m ² the compounds -1 (Gelatin dispersion) 100mg / m ²

A coated sample was prepared as described above.

(Composition of Processing Solution) The composition of the developing solution is shown below. Diethylenetriamine-pentaacetic acid 2.0 g Sodium carbonate 5.0 g Boric acid 10.0 g Potassium sulfite 85.0 g Sodium bromide 6.0 g Diethylene glycol 40.0 g 5-Methylbenzotriazole 0.2 g 2-Mercaptobenzimidazole-5-sulfonic acid Soda 0.3 g Hydroquinone 30.0 g 4-Hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone 1.6 g Compound shown in Table 1 0.1 mol / L Potassium hydroxide was added, and water was added. The liter was adjusted to 1 liter and the pH was adjusted to 10.7.

500 ml of the developing solution was put into a 1000 ml beaker, the beaker was covered with Saran wrap, a hole having a diameter of 2 mm was made in the cover, and the cover was left at room temperature for 10 days. Thereafter, the remaining amount of hydroquinone and the pH value were measured. The results are shown in Table 1.

[0101]

[Table 1]

The fixing solution had the following composition. Ethylenediamine-4acetic acid-2Na salt 0.025 g Sodium sulfite 7.0 g Sodium metabisulfite 20.0 g Sodium thiosulfate pentahydrate 300.0 g Water is added to make 1 liter to pH 5.7. 1 liter

(Evaluation of photographic properties) 488 using film A
The film was exposed to xenon flash light having an emission time of 10 ⁻⁶ sec with an interference filter having a peak at nm and a continuous wedge intervening. This exposed sample was treated with a new solution of the above-described developer and a temporal solution left at room temperature for 10 days.
An amount sufficient for development processing with G-710NH was prepared and developed.

The developing conditions are as follows. Development 38 ° C 12.3 seconds Fixing 37 ° C 12.2 seconds Washing 26 ° C 6.6 seconds Drying 55 ° C 13.3 seconds

The photographic properties were evaluated as follows. The gradation was expressed by a value obtained by dividing the difference between the density of 3.0 and the density of 0.1 by the difference between the logarithm of the exposure amount giving the density of 3.0 and the logarithm of the exposure amount giving the density of 0.1. The sensitivity was 1.5% when the light-sensitive material was processed with a blank developing solution containing no additive compound.
And the reciprocal of the amount of exposure required to obtain was relatively set as 100. Table 2 shows the results of photographic properties when a new developer solution and an aged solution were used.

[0106]

[Table 2]

As can be seen from Tables 1 and 2, when the compound of the present invention is used, decomposition of hydroquinone and fluctuation of pH due to fatigue with time due to air oxidation are small, and fluctuation of photographic properties (sensitivity, gradation) is small. Stable development processing became possible.

Example 2 (First Photosensitive Emulsion Layer) Preparation of Photosensitive Emulsion A A 0.37 M aqueous silver nitrate solution and 1 × 10 5 per mol of silver were used.
^-7 mol of (NH ₄ ) ₃ RhCl ₆ and 5 × 10 ^-7 mol of K ₃ Ir
The halogen salt aqueous solution containing sodium chloride potassium bromide and 0.27M of Cl ₆ 0.11 M, sodium chloride,
To the aqueous gelatin solution containing 1,3-dimethyl-2-imidazolidinethione was added by stirring by a double jet method at 45 ° C. for 12 minutes while stirring, and the average particle size was 0.20.
Nucleation was carried out by obtaining silver chlorobromide particles having a particle diameter of 70 μm and a silver chloride content of 70 mol%. Subsequently, a 0.63 M silver nitrate aqueous solution, 0.19 M potassium bromide, 0.4
A halogen salt aqueous solution containing 7M sodium chloride was added by a double jet method over 20 minutes. Then one
A conversion was performed by adding a KI solution of × 10 ^-3 mol, and the mixture was washed by a flocculation method according to a conventional method. 40 g of gelatin was added to adjust the pH and pAg to 7.5. Further, 5 mg of sodium thiosulfate per mol of silver was added. , 8 mg of chloroauric acid and 7 mg of sodium benzenethiosulfonate, heated at 60 ° C. for 45 minutes, subjected to a chemical sensitization treatment, and 4-hydroxy-6-methyl-1,
150 mg of 3,3a, 7-tetrazaindene, proxel and phenoxyethanol were added. The resulting grains were silver chlorobromide cubic grains having an average grain size of 0.28 μm and a silver chloride content of 70 mol%. (Variation coefficient 9%)

Coating of First Photosensitive Emulsion Layer These emulsions were divided and used as sensitizing dyes in an amount of 1 × 10 ^-3 mol of 5- [3- (4-sulfobutyl) -5 per mol of silver.
-Chloro-2-benzoxazolidylidene] -1-hydroxyethoxyethyl-3- (2-pyridyl) -2-thiohydantoin potassium salt, and 2 × 10 ^-4 mol of 1-phenyl-5-mercapto Tetrazole, 5x
^10-4 moles of a short-wave cyanine dye of the compound (a) represented by the following structural formula and a polymer of the compound (b) (200 mg /
m ^2), hydroquinone (50 mg / m ²⁾ and a dispersion of polyethyl acrylate (200mg / m ^2), 1,3- bis-vinylsulfonyl-2-propanol as a hardening agent (2
00 mg / m ² ) and the following hydrazine compound (c) were added, and the mixture was coated so that the coated silver amount was 3.6 g / m ² and the gelatin was 2.0 g / m ² .

[0110]

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(Coating of Intermediate Layer) Gelatin 1.0 g / m ² 1,3-bisvinylsulfonyl-2-propanol 4.0 wt% to gelatin

(Second Photosensitive Emulsion Layer) Preparation of Photosensitive Emulsion B A 1.0 M silver nitrate aqueous solution and 3 × 10 ⁻⁷ per mol of silver were used.
An aqueous halide solution containing molar (NH ₄ ) ₃ RhCl ₆ , containing 0.3 M potassium bromide and 0.74 M sodium chloride, containing sodium chloride and 1,3-dimethyl-2-imidazolidinthione Added to the aqueous gelatin solution by double jet method at 45 ° C. for 30 minutes while stirring,
Average grain size 0.28 µm, silver chloride content 70 mol%
Of silver chlorobromide particles were obtained. Thereafter, it was washed with flocculation according to a conventional method, and 40 g of gelatin was added.
6.5 and pAg 7.5, and 5 mg of sodium thiosulfate and 8 mg of chloroauric acid per 1 mol of silver were added.
The mixture was heated at 60 ° C. for 60 minutes for chemical sensitization, and 150 mg of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added as a stabilizer. The resulting grains were silver chlorobromide cubic grains having an average grain size of 0.28 μm and a silver chloride content of 70 mol%. (Coefficient of variation 10%)

Coating of Second Photosensitive Emulsion Layer Photosensitive emulsion B was re-dissolved, and at 40 ° C., 1.0 × 10 ⁻³ mol of 5- [3- (4- Sulfobutyl) -5-chloro-2-benzooxazolidylidene] -1-hydroxyethoxyethyl-3- (2-pyridyl) -2-thiohydantoin potassium salt and 1.0 ×
10 ^-3 mol of a KI solution was added, and a dispersion of 2 × 10 ^-4 mol of 1-phenyl-5-mercaptotetrazole and polyethylacrylate was added at 50 mg / m ² , and 1,3-bisvinylsulfonyl was used as a hardener. 4.0 wt% of 2-propanol based on gelatin, the following redox compound 1.0
× 10 ^-4 mol / m ^{2 was} added, and coating was performed so that the coated silver amount was 0.2 g / m ² and the gelatin was 0.3 g / m ² .

[0114]

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(Coating of protective layer)
Gelatin 1.0 g / m ² and polymethyl methacrylate particles (average particle size 2.5 μ) 0.3 g / m ² were coated using the following surfactants.

[0116]

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The back layer and the back protective layer were applied according to the following formulation. [Back layer formulation] Gelatin 3 g / m ² latex Polyethyl acrylate 2 g / m ² Surfactant Sodium p-dodecylbenzenesulfonate 40 mg / m ²

[0118]

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Dye, mixture of dyes [a], [b] and [c] Dye [a] 50 mg / m ² Dye [b] 100 mg / m ² Dye [c] 50 mg / m ²

[0120]

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[Back protective layer] Gelatin 0.8 g / m ² polymethyl methacrylate fine particles (average particle size 4.5 μ) 30 mg / m ² dihexyl-α-sulfosacnate sodium salt 15 mg / m ² dodecylbenzenesulfonic acid sodium salt 15 mg / m ² sodium acetate 40 mg / m ²

[0122]

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On a polyester film (100μ) support, a first photosensitive emulsion layer was provided as a lowermost layer, a second photosensitive emulsion layer containing a redox compound was further provided via an intermediate layer, and a protective layer was simultaneously coated on this layer. A sample C was prepared.

(Composition of Processing Solution) The composition of the developing solution is shown below. Image solution hydroquinone 50.0 g N-methyl-p-aminophenol 0.3 g sodium hydroxide 18.0 g 5-sulfosalicylic acid 30.0 g boric acid 25.0 g potassium sulfite 124.0 g disodium ethylenediaminetetraacetate 1.0 g odor Potassium iodide 10.0 g 5-Methylbenzotriazole 0.4 g Sodium 3- (5-mercaptotetrazole) benzenesulfonate 0.2 g N-n-butyldiethanolamine 15.0 g Sodium toluenesulfonate 8.0 g 2-mercaptobenzimidazole- 0.3 g of sodium 5-sulfonate Compounds shown in Table 3 0.1 mol / l 1 liter 1 liter by adding water Adjust to pH = 11.6 (add potassium hydroxide)
pH 11.6 Each developer was thus adjusted. Developer 5
00 ml was put in a 1000 ml beaker, the beaker was covered with Saran wrap, a 2 mm diameter hole was made in the cover, and the cover was left at room temperature for 5 days.

(Evaluation of Photographic Properties) Film Sample C Obtained
Was exposed through 3200 ° K tungsten light through an optical wedge for sensitometry, and the exposed sample was exposed in the same manner as in Example 1 by using the above-mentioned new solution of the developing solution and the aged solution left at room temperature for 5 days. The processing was performed at 34 ° C. for 30 seconds using a developing machine, and GR-F1 manufactured by Fuji Photo Film Co., Ltd. was used as a fixing solution. Table 3 shows the results of photographic properties when a new developer solution and a time-lapse solution were used.

[0126]

[Table 3]

As can be seen from Table 3, in the developer using the compound of the present invention, high sensitivity and high contrast photographic properties can be sufficiently maintained, and fatigue of the developer over time due to air oxidation is reduced.
The object of the present invention has been achieved.

Example 3 (Preparation of tabular pure silver bromide particles) 6 g of potassium bromide and 7 g of gelatin were added to 1 liter of water, and 37 cc of an aqueous silver nitrate solution (silver nitrate 4 .0
38 g of an aqueous solution containing 0 g) and 5.7 g of potassium bromide was added over 37 seconds by the double jet method. Next, after adding 18.6 g of gelatin, the temperature was raised to 70 ° C., and 89 cc of an aqueous silver nitrate solution (9.8 g of silver nitrate) was added over 22 minutes. Here, 7 cc of 25% ammonia aqueous solution is added,
After physical aging at the same temperature for 10 minutes, 6.5 cc of a 100% acetic acid solution was added. Subsequently, silver nitrate 153.
An aqueous solution containing 0 g and an aqueous solution of potassium bromide were pAg8.
While maintaining at 5, the addition was performed over 35 minutes by the control double jet method. Next, pBr was adjusted to 2.8 using an aqueous silver nitrate solution, and 15 cc of a 2N potassium thiocyanate solution was added. After physical ripening at the same temperature for 5 minutes, the temperature was lowered to 35 ° C. Thus, monodispersed tabular grains having an average projected area diameter of 1.11 μm, a thickness of 0.164 μm, and a diameter variation coefficient of 18.0% were obtained. Thereafter, soluble salts were removed by a sedimentation method. The temperature was raised again to 40 ° C., and 30 g of gelatin, 2.35 g of phenoxyethanol, and sodium polystyrene sulfonate of 0.3 g as a thickener were added.
8 g, pH 5.9 with sodium hydroxide and silver nitrate solution.
0, pAg 8.25.

(Preparation of Emulsion: Chemical Sensitization) Next, the above grains were subjected to chemical sensitization while being kept at 56 ° C. while stirring. First add 0.043 mg of thiourea dioxide and add 20
The mixture was held for 1 minute to perform reduction sensitization. Next, 0.07μm in diameter
Silver iodide fine grains of 0.15 mol% based on the total silver amount, and then 4-hydroxy-6-methyl-1,3,3
a, 7-Tetraazaindene 20 mg and sensitizing dye I
0 mg and 4.2 mg of sensitizing dye II were added. Further, 0.83 g of an aqueous calcium chloride solution was added. Subsequently, 1.3 mg of sodium thiosulfate, 3.4 mg of selenium compound-1, 2.6 mg of chloroauric acid and 90 mg of potassium thiocyanate were added, and after 40 minutes, the mixture was cooled to 35 ° C. Thus, the preparation of an emulsion having a total silver iodide content of 0.15 mol% was completed.

[0130]

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[0131]

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[0132]

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(Preparation of Emulsion Coating Layer) The following chemicals were added to the chemically sensitized emulsion per mole of silver halide to prepare a coating solution (Type A). -2-bis (hydroxyamino) -4-diethylamino-1,3,5-triazine 72 mg-Trimethylolpropane 9 g-Dextran (average molecular weight 39,000) 18.5 g-Potassium polystyrene sulfonate (average molecular weight 600,000) 1.8 g Compound (E-1) 3.4 mg Compound (E-2) 4.8 g Snowtex C (Nissan Chemical Co., Ltd.) 29.1 g Gelatin The total amount applied to one side is 2.4 g / m was prepared ² so as. Hardener (1,2-bis (vinylsulfonylacetamido) ethane) Prepared so that the swelling ratio was 230%.

[0134]

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(Preparation of Surface Protective Layer Coating Solution) A surface protective layer coating solution was prepared and prepared such that each component had the following coating amount. Gelatin 0.966 g / m ² · Sodium polyacrylate (average molecular weight 400,000) 0.023 - Compound (P-1) 0.013 - Compound (P-2) 0.045 - Compound (P-3) 0 0.0065 Compound (P-4) 0.003 Compound (P-5) 0.001 Compound (P-6) 0.0012 Polymethyl methacrylate (average particle size 3.7 μm) 0.087 Proxel 0 0.0005 (adjusted to pH 7.4 with NaOH)

[0136]

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(Preparation of Support) (1) Preparation of Dye K for Undercoat Layer The following dye was ball-milled by the method described in JP-A-63-197943.

[0138]

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434 ml of water and Triton X200® surfactant (6.7% of TX-200®)
791 ml of a 1% aqueous solution was placed in a 2 liter ball mill. 20 g of the dye were added to this solution. 400 ml (2 mm diameter) beads of zirconium oxide (ZrO) were added and the contents were ground for 4 days. After this, 12.5% gelatin 16
0 g was added. After defoaming, the ZrO beads were removed by filtration. When observing the obtained dye dispersion,
The particle size of the pulverized dye has a wide distribution ranging from 0.05 to 1.15 μm in diameter, and the average particle size is 0.37 μm.
m. Furthermore, dye particles having a size of 0.9 μm or more were removed by centrifugation. Thus, a dye dispersion K was obtained.

(2) Preparation of Support A corona discharge treatment was performed on a biaxially stretched polyethylene terephthalate film having a thickness of 183 μm, and a first undercoating liquid having the following composition was applied in an amount of 5.1 cc / m ² . It was applied by a wire bar coater and dried at 175 ° C. for 1 minute. Next, a first undercoat layer was similarly provided on the opposite surface. The polyethylene terephthalate used contained a dye having the following structure at 0.04% by weight.

[0141]

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• Butadiene-styrene copolymer latex solution (solid content 40% butadiene / styrene weight ratio = 31/36 79 cc) • 4,4-dichloro-6-hydroxy-s-triazine sodium salt 4% solution 5 cc-distilled water 900.5 cc * The following emulsifying dispersant was used in the latex solution.

[0143]

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A second undercoat layer having the following composition was coated on each of the first undercoat layers on both sides by a wire bar coater method on each side such that the coating amount was as described below. Coated and dried at ℃.・ Gelatin 160 mg / m ²・ Dye dispersion K (26 mg / m ² as a solid dye)

[0145]

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(Preparation of photographic material) The emulsion layer and the surface protective layer were coated on both sides of the support prepared as described above by a simultaneous extrusion method. The amount of silver applied per side is 1.75g
/ M ² . Thus, a photographic material was obtained.

[Processing] An automatic developing machine: CEPROS manufactured by FUJIFILM Corporation was modified to increase the transport speed. Preparation of Concentrated Solution <Developer> Parts A potassium hydroxide 330 g potassium sulfite 630 g sodium sulfite 255 g potassium carbonate 90 g boric acid 45 g diethylene glycol 180 g diethylenetriaminepentaacetic acid 30 g 1- (N, N-diethylamine) ethyl-5-mercaptotetrazole 75 g Hydroquinone 450 g 4-Hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone 60 g Compound shown in Table 4 0.1 mol / L Water was added to add 4125 mL

Parts agent B Diethylene glycol 525 g 3,3'-dithiobishydrocinnamic acid 3 g Glacial acetic acid 102.6 g 2-nitroindazole 3.75 g 1-phenyl-3-pyrazolidone 34.5 g Water was added and 750 ml

Parts agent C Glutaraldehyde (50 wt / wt%) 150 g Potassium bromide 15 g Potassium metabisulfite 105 g Add water 750 ml

<Fixing Solution> Ammonium thiosulfate (70 wt / vol%) 3000 ml Ethylenediaminetetraacetic acid disodium dihydrate 0.45 g sodium sulfite 225 g boric acid 60 g 1- (N, N-diethylamine) -ethyl-5-mercapto Tetrazole 15 g Tartaric acid 48 g Glacial acetic acid 675 g Sodium hydroxide 225 g Sulfuric acid (36N) 58.5 g Aluminum sulfate 150 g Water is added 6000 ml pH 4.68

(Preparation of Processing Solution) The above-mentioned developer concentration solution was filled into the following containers for each part. In this container, the respective partial containers of the parts agents A, B, and C are connected together by the container itself. The above-mentioned fixer concentration was also filled in the same type of container. First, as a starter in the developing tank,
Aqueous solution 30 containing 54 g of acetic acid and 55.5 g of potassium bromide
0 ml was added. Insert the processing agent container upside down and insert it into the perforation blade of the processing liquid stock tank mounted on the side of the automatic processing machine, break the sealing film of the cap, and transfer each processing agent in the container to the stock tank. Filled. These processing agents were filled in the developing tank and the fixing tank of the automatic processing machine at the following ratios by operating the pumps respectively installed in the automatic processing apparatus. Also,
Each time the photosensitive material was processed into eight pieces in terms of the size of a quarter, the stock solution of the processing agent and water were mixed at this ratio and replenished into the processing tank of the automatic processing machine.

Developing solution Part solution A 55 ml Part solution B 10 ml Part solution C 10 ml Water 125 ml pH 10.50 Fixer Concentration 80 ml Water 120 ml pH 4.62 The washing tank was filled with tap water.

As a scale inhibitor, 0.4 g of actinobacteria supported on pearlite having an average particle diameter of 100 μm and an average pore diameter of 3 μm was covered with a polyethylene pin (the pin opening was covered with a 300-mesh nylon cloth. 3 pieces of water and bacteria can be distributed from the cloth), two of them are placed at the bottom of the washing tank and one is placed at the bottom of the washing tank (0.2 liter). Each sunk. Processing speed and processing temperature Current image 35 ° C 8.8 seconds Fixing 32 ° C 7.7 Washing 17 ° C 3.8 squeeze
4.4 Drying 58 ℃ 5.3 Total 30 Replenishment amount Developer 25ml / 10 × 12inch Fixer 25ml / 10 × 12inch

(Evaluation of Photographic Properties) The processing speed of the automatic developing machine was set to Dry to Dry 30 seconds, and the photographic properties of the new developing solution were evaluated first. Subsequently, the developing solution was aged using an automatic developing machine. That is, the photographic properties of the aged solution which had been temperature-controlled for 12 hours per day and aged for 3 weeks were evaluated again. X-ray orthoscreen HR- manufactured by Fuji Photo Film Co., Ltd.
4 was used to give a 0.05 second exposure from both sides. After exposure, the following processing was performed to evaluate the sensitivity. The gradation was represented by a value obtained by dividing the difference between the density of fog + 0.25 and the density of fog + 2.0 by the logarithm of the exposure amount giving each density. The sensitivity was relatively expressed as the reciprocal of the exposure required to obtain a density of fog + 1.0 when the photographic material was processed with a blank developing solution containing no added compound, as 100. Dm represents the maximum density. Table 4 shows the results of the photographic properties.

[0155]

[Table 4]

As can be seen from Table 4, in the developer using the compound of the present invention, fog was small, Dm was given a sufficient density, and high sensitivity and high photographic properties were sufficiently maintained. The goal has been achieved.

Example 4 (Preparation of silver halide emulsion) 34 g of gelatin was dissolved in 850 ml of H ₂ O, and 1.7 g of sodium chloride, 0.1 g of potassium bromide and the following compound were placed in a vessel heated to 65 ° C. (A)

[0158]

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After adding 70 mg, 500 ml of an aqueous solution containing 170 g of silver nitrate, potassium hexachloroiridate (III) so that the molar ratio of iridium to the finished silver halide is 5 × 10 ^-7 , 12 g of sodium chloride and 12 g of bromide Cubic monodispersed silver chlorobromide particles having an average particle size of 0.4 μm were prepared by adding 500 ml of a water-soluble solution containing 98 g of potassium by a double jet method. After desalting this emulsion, 50 g of gelatin was added, pH 6.5, pAg 8.1.
2.5mg of sodium thiosulfate and 5mg of chloroauric acid
Was added thereto, and the mixture was chemically sensitized at 60 ° C., and then 0.2 g of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added, followed by quenching and solidification (emulsion A). Next, 0.3 μm cubic monodispersed silver chlorobromide particles were prepared in the same manner as in Emulsion A except that the temperature of the gelatin solution was changed to 40 ° C.
After desalting treatment, 50 g of gelatin was added, pH 6.5, pA
g8.1. To this emulsion were added 2.5 mg of sodium thiosulfate and 5 mg of chloroauric acid, and after chemical sensitization at 65 ° C, 4-hydroxy-6-methyl-1,3,3a, 7-
Emulsion B was prepared by quenching and solidifying by adding 0.2 g of tetrazaindene.

Emulsions (A) and (B) were mixed at a weight ratio of 1: 1, and the following additives were added per mol of silver halide to prepare an emulsion coating solution.

(Formulation of emulsion coating solution)

A. Spectral sensitizing dye [2] 1.0 × 10 ^-4 mol b. Supersensitizer [3] 0.7 × 10 ^-3 mol c. Preservability improver [4] 1 × 10 ^-3 mol d. Polyacrylamide (molecular weight 40,000) 10 g e. Dextran 10g f. Trimethylolpropane 1.6 g g. 1.2 g of sodium polystyrene sulfonate 12 g of latex of poly (ethyl acrylate / methacrylic acid) N, N'-ethylenebis- (vinylsulfoneacetamide) 3.0 g 1-phenyl-5-mercapto-tetrazole 50 mg {. Stabilizer

[9] 100mg

Spectral sensitizing dye [2]

[0164]

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Supersensitizer [3]

[0166]

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Preservability improver [4]

[0168]

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Stabilizer

[9]

[0170]

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(Preparation of Coating Solution for Surface Protective Layer of Emulsion Layer)

The container was heated to 40 ° C., and additives were added according to the following formulation to prepare a coating solution.

(Formulation of Coating Solution for Surface Protective Layer of Emulsion Layer)

A. Gelatin 100 g d. Polyacrylamide (molecular weight 40,000) 12 g c. Polystyrene sodium sulfonate (molecular weight: 600,000) 0.6 g D, N, N'-ethylenebis- (vinylsulfoneacetamide) 2.2 g E. 2.7 g of polymethyl methacrylate fine particles (average particle size: 2.0 μm) Sodium t-octylphenoxyethoxyethanesulfonate 1.8 g g. _{C 16 H 33 O- (CH 2} CH 2 O) 10 -H 4.0g Ji. Sodium polyacrylate 6.0 g C ₈ F ₁₇ SO ₃ K 70mg j. _{C 8 F 17 SO 2 N (} C 3 H 7) (CH 2 CH 2 O) 4 (CH 2) 4 -SO 3 Na 70mg Le. NaOH (1N) 6 ml III. 90 ml of methanol 1-phenyl-5-mercapto-tetrazole 80 mg Compound [5] 0.06 g

[0175]

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(Preparation of Back Layer Coating Solution) A container was heated to 40 ° C., and additives were added according to the following formulation to prepare a back layer coating solution.

(Formulation of Coating Solution for Back Layer) a. Gelatin 100g b. Dye [6] 4.2 g c. 1.2 g of sodium polystyrene sulfonate d. Poly (ethyl acrylate / methacrylic acid) latex 5 g e. N, N'-ethylenebis- (vinylsulfoneacetamide) 4.8 g f. Compound [5] 0.06 g g. Dye [7] 0.3 g h. Dye [8] 0.05 g Colloidal silica 15g

Dye [6]

[0179]

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Dye [7]

[0181]

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Dye [8]

[0183]

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(Preparation of Coating Solution for Back Surface Protective Layer)

The container was heated to 40 ° C., and additives were added according to the following formulation to prepare a coating solution.

(Formulation of Coating Solution for Back Surface Protective Layer)

A. Gelatin 100g b. 0.5 g of polystyrene sulfonate soda c. N, N'-ethylenebis- (vinylsulfoneacetamide) 1.9 g d. Polymethyl methacrylate fine particles (average particle size 4.0 μm) 4 g e. sodium t-octylphenoxyethoxyethanesulfonate 2.0 g f. NaOH (1N) 6 ml g. Sodium polyacrylate 2.4 g h. _{C 16 H 33 O- (CH 2} CH 2 O) 10 -H 4.0g Li. C ₈ F ₁₇ SO ₃ K 70 mg _{C 8 F 17 SO 2 N (} C 3 H 7) (CH 2 CH 2 O) 4 (CH2) 4 -SO 3 Na 70mg Le. Methanol 150 ml III. Compound [5] 0.06 g

(Preparation of photographic material) The above-mentioned coating solution for the back layer together with the coating solution for the surface protective layer of the back layer was coated on one side of the polyethylene terephthalate support so that the total coating amount of gelatin was 3.0 g / m ^2. Applied. Subsequently, on the opposite side of the support, the above-mentioned emulsion coating solution and surface protective layer coating solution were coated with a total silver coating amount of 2.3 g / m ² and a gelatin coating amount of the surface protective layer of 1.0 g / m ^2. An application sample was prepared so as to obtain m ² . The sensitivity of each single emulsion was measured based on the sensitometric method shown below.

<Developer composition> KOH 57.5 g Na ₂ SO ₃ 87.5 g K ₂ SO ₃ 110 g diethylenetriaminepentaacetic acid 5 g boric acid 25 g K ₂ CO ₃ 32.5 g hydroquinone 87.5 g diethylene glycol 125 g 4-hydroxymethyl-4- Methyl-1-phenyl 10 g-3-pyrazolidone 5-methylbenzotriazole 0.15 g 2,3,5,6,7,8-hexahydro-2-thioxo 0.25 g -4 (1H) quinazolinone 2-mercaptobenzimidazole- 5-Sulfonic acid 0.35 g Sodium KBr 7.5 g 1-Phenyl-5-mercapto-tetrazole 0.15 g Compound shown in Table 5 0.1 mol / L Water was added 2.5 L <Fixing solution composition> Thio Ammonium sulfate 145g Ethylenediamine Disodium tetraacetate dihydrate 30 mg Na ₂ S ₂ O ₃ .5H ₂ O 15 g Sodium metabisulfite 13.3 g NaOH 12.6 g Acetic acid (90% by weight) 30 g KI 0.5 g Add water to 1 liter

(Method of evaluating photographic properties) Using the photographic material prepared by the above method, sensitometry was performed by the following method, and sensitivity and gamma were measured. Photographic materials at 25 ° C 60
% For 7 days after application, and 780 at room temperature.
nm semiconductor laser (F from Fuji Photo Film Co., Ltd.)
CR7000 Laser Image Printer type CR-LP4
Scanning exposure is performed using 14), and the company's FCR
Using a 7000 type automatic developing machine, the developing temperature was 35 ° C., the conveying speed was 1,400 mm / min, and the developing process was carried out for 30 seconds from dry to dry by modifying the automatic developing machine so that the conveying speed could be changed.

First, the photographic properties of the new developing solution were evaluated. Subsequently, the developing solution was aged using an automatic developing machine. That is, the photographic properties of the aged solution which had been temperature-controlled for 12 hours per day and aged for 3 weeks were evaluated again. The gradation was expressed by a value obtained by dividing the difference between the density of fog + 0.8 and the density of fog + 2.0 by the difference of the logarithm of the exposure amount giving each density. The sensitivity was relatively expressed as the reciprocal of the exposure required to obtain a density of fog + 1.0 when the photographic material was processed with a blank developing solution containing no added compound, as 100. Table 5 shows the results of photographic properties when a new developing solution and an aged solution were used.

[0192]

[Table 5]

As can be seen from Table 5, the developer using the compound of the present invention was able to sufficiently maintain high sensitivity and high contrast photographic properties, and the object of the present invention was achieved.

[0194]

By using the compound of the present invention in a developer, the air oxidation stability of a black-and-white developer of a silver halide photographic material can be remarkably improved. Therefore, the replenishment of the developer can be reduced, the pollution load can be reduced, and stable and high-quality image can be provided.

Continuation of the front page (56) References JP-A-57-141643 (JP, A) JP-A-4-32838 (JP, A) JP-A-2-300747 (JP, A) JP-A-56-106244 (JP) , A) JP-A-2-21037 (JP, A) JP-B-48-43137 (JP, B1) (58) Fields investigated (Int. Cl. ⁶ , DB name) G03C 5/305

Claims (3)

(57) [Claims] 1. A method for forming an image of an exposed silver halide photographic material through a developing process and a fixed deposition process, comprising: a developer containing at least one compound represented by the following general formula (A): A method for processing a silver halide photographic light-sensitive material, comprising: General formula (A) In the formula, R ₁ and R ₂ each represent a hydroxy group, X is composed of a carbon atom or a nitrogen atom, and X is 5 to 5 in combination with the two vinyl carbons and the carbonyl carbon substituted by R ₁ and R _2. Construct a 6-membered ring. 2. A developer composition comprising at least one compound represented by the following general formula (A). General formula (A) In the formula, R ₁ and R ₂ each represent a hydroxy group, X is composed of a carbon atom or a nitrogen atom, and X is 5 to 5 in combination with the two vinyl carbons and the carbonyl carbon substituted by R ₁ and R _2. Construct a 6-membered ring. 3. A method for forming an image of an exposed silver halide photographic material through a developing process and a fixed deposition process, wherein at least (a) at least one compound represented by the following general formula (A) is used. (A) In the formula, R ₁ and R ₂ each represent a hydroxy group, X is composed of a carbon atom or a nitrogen atom, and X is 5 to 5 in combination with the two vinyl carbons and the carbonyl carbon substituted by R ₁ and R _2. Construct a 6-membered ring. (B) a dihydroxybenzene-based developing agent (c) a free sulfite of 0.3 mol / l or more (d) a developing solution containing a 1-phenyl-3-pyrazolidone-based developing agent and / or an aminophenol-based developing agent A method for developing a silver halide light-sensitive material.